WO2015046561A1 - Surface-treated ito conductive film and method for producing same - Google Patents

Surface-treated ito conductive film and method for producing same Download PDF

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WO2015046561A1
WO2015046561A1 PCT/JP2014/076039 JP2014076039W WO2015046561A1 WO 2015046561 A1 WO2015046561 A1 WO 2015046561A1 JP 2014076039 W JP2014076039 W JP 2014076039W WO 2015046561 A1 WO2015046561 A1 WO 2015046561A1
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conductive film
ito
surface treatment
ito conductive
carbon atoms
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PCT/JP2014/076039
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French (fr)
Japanese (ja)
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岳洋 米澤
山崎　和彦
愛 竹之下
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三菱マテリアル株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Definitions

  • the present invention relates to a surface-treated ITO conductive film capable of suppressing an increase in electric resistance value under high temperature and high humidity and a method for producing the same.
  • ITO refers to indium tin oxide.
  • Transparent electrodes are used in display devices such as LCD (Liquid Crystal Display), PDP (Plasma Display Panel), organic EL (ElectroLuminescence), and touch panel.
  • This transparent electrode is often composed of a transparent conductive material made of ITO or the like.
  • Such a transparent electrode is usually formed into a film by a sputtering method or the like (see, for example, Patent Document 1).
  • the sputtering apparatus is expensive and has a problem that the film formation efficiency is low and the film is easily cracked.
  • a method of forming an ITO conductive film excellent in flexibility, which is less prone to cracking a method of applying an ITO conductive film forming coating to a substrate instead of the sputtering method has been proposed.
  • the transparent electrode obtained by the coating method is placed under high temperature and high humidity, the electrical resistance value tends to increase due to oxygen and moisture in the atmosphere. It was.
  • a surface-treated conductive powder and a curable compound obtained by treating the surface of a conductive powder such as ITO powder having water resistance with a surface treatment agent Transparent conductive materials (for example, see Patent Document 2), transparent conductive materials containing transparent conductive particles such as resin, ITO powder, silica material, and silane coupling agent (for example, see Patent Document 3) have been proposed. ing.
  • JP 2004-315951 A (paragraph [0002]) JP 2006-59772 A (summary, claim 1) JP 2009-135044 (Abstract, Claim 1)
  • the transparent electrode of the ITO conductive film formed of the transparent conductive material disclosed in Patent Documents 2 and 3 can suppress an increase in electrical resistance value due to the influence of moisture even under high temperature and high humidity.
  • the conventional high temperature and high humidity shown here is, for example, a temperature of 60 ° C., a humidity of 95% RH, and 750 hours.
  • the use of transparent electrodes has become more diverse, and there has been a demand for an ITO conductive film that can suppress an increase in the electrical resistance value of a transparent electrode under high temperature and high humidity even under severer conditions than before. ing.
  • An object of the present invention is to provide a surface-treated ITO conductive film which is a transparent electrode capable of suppressing an increase in electrical resistance value under high temperature and high humidity even under severer conditions than before, and a method for producing the same There is to do.
  • a surface treatment agent comprising a silicate ester having 4 alkoxy groups having 2 or less carbon atoms or an oligomer of the silicate ester, or 2 alkoxy groups having 2 or less carbon atoms.
  • a second aspect of the present invention is the invention based on the first aspect, wherein the silicate ester further comprises tetramethoxysilane having an alkyl group having 1 carbon atom or tetraethoxy having an alkyl group having 2 carbon atoms. Silane.
  • a third aspect of the present invention is the invention based on the first aspect, wherein the silane coupling agent is N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxy.
  • the silane coupling agent is N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxy.
  • a vapor of a surface treatment solution in which a surface treatment agent based on any one of the first to third aspects is dissolved in a solvent is exposed in a vapor phase to an ITO conductive film in a container.
  • an ITO conductive film by applying a surface treatment solution obtained by dissolving a surface treatment agent based on any one of the first to third aspects in a solvent to the surface of the ITO conductive film. It is a manufacturing method of the ITO electrically conductive film which processes the surface, It is characterized by the above-mentioned.
  • a sixth aspect of the present invention is an invention based on the fifth aspect, wherein the surface treatment liquid is applied to the surface of the ITO conductive film by a spin coat method or a dip coat method. It is.
  • the main component of ITO In 2 O 3
  • has a Bixbyite structure and can be expressed as a structure in which oxygen is regularly removed from the fluorite structure.
  • This structure has a structure in which oxygen is easily taken in between lattices when the amount of Sn as a dopant is increased. For this reason, when the ITO conductive film is placed under high temperature and high humidity, water adsorbed on the surface of the conductive film is bonded as —OH between oxygen vacancies and lattices on the surface of the ITO powder constituting the conductive film, and traps carrier electrons. Therefore, the conductivity of the ITO conductive film is reduced.
  • the ITO conductive film according to the first aspect of the present invention is treated with the specific surface treatment agent described above.
  • the surface treatment agent is the silicate ester
  • the silane coupling agent the stability to water is greatly improved by bonding an amino group or a mercapto group between oxygen vacancies or lattices on the surface of the ITO powder constituting the conductive film. it is conceivable that.
  • —OH already exists on the particle surface.
  • the conductive film of the present invention can suppress an increase in electrical resistance value under high temperature and high humidity.
  • tetramethoxysilane having an alkyl group having 1 carbon atom or tetraethoxysilane having an alkyl group having 2 carbon atoms is selected as the silicate ester. Since these silicate esters have a small number of carbon atoms, the reactivity increases. As a result, there is an effect that the silicate ester is easily bonded to the ITO surface.
  • N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxy are used as silane coupling agents. Any one selected from the group consisting of silane, 3-mercaptopropyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and decyltrimethoxysilane is selected.
  • These silane coupling agents have an effect of inhibiting H 2 O from approaching the ITO surface because of the steric hindrance and polarity of the end groups.
  • ⁇ ITO powder> 1A and 1B show an example of ITO powder that is a material for forming the ITO conductive film of the present invention.
  • the ITO conductive film of the present invention can be formed of ITO powder produced by other methods without using this ITO powder.
  • the ITO powder is composed of polycrystalline ITO particles 10.
  • the polycrystalline ITO particles 10 are composed of a rod-shaped central core 11 and a plurality of rod-shaped bodies 12, and are integrally formed with the rod-shaped body 12 so as to surround the rod-shaped central core 11 along the same direction in the longitudinal direction of the rod-shaped central core 11. Is formed.
  • a plurality of short rods are observed as twigs, and these short rods are adjacent to each other while surrounding the rod-shaped central core. It is observed that they stick to the rod-shaped central core side by side in the same direction.
  • the diameters and lengths of the plurality of rod-shaped bodies are not necessarily the same, and the cross-sectional shape and the surface shape are not necessarily the same.
  • the average length L in the longitudinal direction of the rod-shaped central core 12 of the polycrystalline ITO particle 10 is in the range of 0.2 to 5.0 ⁇ m, preferably 1.0 to 5.0 ⁇ m.
  • L / D is in the range of 2 to 20, preferably 3 to 10. It is in.
  • L is less than 0.2 ⁇ m, it becomes easy to stand perpendicular to the substrate surface on which the ITO conductive film is formed, and the effect of being easily overturned like a rugby ball cannot be obtained.
  • L exceeds 5.0 ⁇ m the packing between the particles is deteriorated. If L / D is less than 2, the effect of improving conductivity due to anisotropy cannot be obtained. If L / D is more than 20, the rod-like particles are broken and shortened when the coating film is produced.
  • the polycrystalline ITO particles have the above-mentioned shape, for example, when a coated ITO film is produced using the polycrystalline ITO particles, when the paint containing the ITO powder is applied to a resin film, or when the paint is applied When the surface is pressurized, the polycrystalline ITO particles are easily oriented on the resin film surface along the coating direction. That is, the polycrystalline ITO particles are easy to roll and lie on the resin film surface. Further, since the ITO particles are polycrystalline, an appropriate shift occurs at the grain boundaries. As a result, voids between the particles are easily filled, and the polycrystalline ITO particles are dense.
  • the conductive film which is a transparent electrode is formed using the ITO particles, the electrical resistance of the conductive film is further lowered and good conductivity is obtained.
  • the coating layer becomes a dense structure. The light transmittance of the conductive film which is a transparent electrode of the optical device can be improved, and haze can be reduced.
  • a tin salt and an indium salt are weighed and mixed at a predetermined ratio, the mixture is dissolved in pure water to obtain a mixed solution of a tin salt and an indium salt, and the mixed solution and an alkali are mixed. React to produce a suspension of tin-containing indium hydroxide.
  • a mixing method a method of adding an alkali such as ammonia to a mixed aqueous solution of a tin salt and an indium salt and reacting them is preferable.
  • anisotropic particles are likely to be generated, and the generated water is controlled by controlling the temperature, the addition rate and / or the particle concentration during the addition of the alkali.
  • the size and axial ratio of the oxide particles can be controlled.
  • the reaction liquid being mixed is irradiated with ultrasonic waves having a predetermined frequency.
  • a plurality of ITO rods shorter than the ITO rod-shaped central core are arranged around the ITO rod-shaped central core along the same direction as the longitudinal direction of the ITO rod-shaped central core and surround the ITO rod-shaped central core.
  • An ITO powder composed of integrally formed polycrystalline ITO particles can be produced.
  • the frequency of the ultrasonic wave is 20 to 10,000 kHz. If the frequency is less than 20 kHz, the ultrasonic stirring effect is weak. On the other hand, if it exceeds 10,000 kHz, the output of the ultrasonic wave is lowered and a sufficient effect cannot be obtained.
  • the frequency is further preferably 20 to 1000 kHz.
  • the predetermined time for applying the ultrasonic wave to the suspension is necessary to appropriately adjust the predetermined time for applying the ultrasonic wave to the suspension according to the frequency, the volume of the neutralizing solution, and the like.
  • the frequency of the ultrasonic wave is 100 kHz and the volume of the reaction solution is 1 L
  • the time for dropping the alkali while irradiating the ultrasonic wave is preferably 20 to 600 minutes. If the application time of the ultrasonic wave is too short, there is a problem that the effect of ultrasonic irradiation cannot be sufficiently obtained, and if it is too long, there is a problem that the particles become too long.
  • the liquid level of the reaction liquid is set to be the same as the liquid level of the ultrasonic irradiation apparatus (medium for transmitting ultrasonic waves from the irradiation apparatus to the reactor) so that the ultrasonic waves are uniformly applied to the reaction liquid.
  • This ultrasonic wave By applying this ultrasonic wave, agglomeration of single pieces of anisotropic ITO particles is prevented, and at the same time, a plurality of ITO rods shorter than the central core around the ITO rod central core are the same as the longitudinal direction of the ITO rod central core. Polycrystalline ITO particles fixed along the direction and surrounding the ITO rod-like central core can be obtained.
  • hydrochloride As the salt of tin and indium, there are hydrochloride, sulfate, nitrate, etc., but hydrochloride is generally preferable.
  • alkali ammonia, caustic soda, caustic potash, or a carbonate thereof is used, but ammonia is preferably used from the viewpoint of reducing impurities after the slurry formation of tin-containing indium hydroxide.
  • the produced tin-containing indium hydroxide slurry is collected by solid-liquid separation of the suspension, and the impurities are washed with pure water to obtain a tin-containing indium hydroxide cake with increased purity.
  • the obtained cake is dried at a temperature of room temperature or higher, preferably 80 ° C. or higher, whereby a dry powder of tin-containing indium hydroxide is obtained.
  • tin may be substituted for indium in indium hydroxide, but may be co-precipitated with indium hydroxide as tin oxide and / or tin hydroxide.
  • the mixture is in the form of indium hydroxide and amorphous as tin hydroxide.
  • the particle diameter of the tin-containing indium hydroxide is determined in the step of obtaining a hydroxide.
  • the reaction temperature is in the range of 40 to 90 ° C.
  • the reaction time is in the range of 20 to 600 minutes
  • the final particle concentration is in the range of 0.01 to 3 mol / liter.
  • the reaction temperature is 60 ° C.
  • the reaction time The time required for total neutralization
  • the final particle concentration may be 0.5 mol / liter.
  • the reaction temperature may be set low, the reaction rate may be shortened, or the particle concentration may be increased.
  • the size of the finally produced polycrystalline ITO particles is substantially determined by the size of the tin-containing hydroxide. That is, when the tin-containing hydroxide changes to ITO particles, both the average length L and the average diameter D shrink about 70 to 80%.
  • this firing step is to generate ITO as an oxide from tin-containing indium hydroxide and to give oxygen deficiency to the resulting ITO crystals. Therefore, this firing step is performed in a weak reducing atmosphere in which an inert gas and a reducing gas are mixed to give oxygen deficiency to the ITO crystal.
  • a weak reducing atmosphere a mixed gas in which hydrogen, carbon monoxide, ammonia gas, or alcohol is mixed with an inert gas such as nitrogen, helium, or argon is used.
  • the mixing ratio of each gas in the mixed gas is appropriately determined by the amount of oxygen deficiency to be imparted to the ITO crystal. However, if the reducing power of the mixed gas is too strong, the tin-containing indium hydroxide becomes InO, metal In, or the like.
  • the mixing ratio of hydrogen, carbon monoxide, or the like is desirably set to such a concentration that the mixed gas does not exceed the explosion limit in the atmosphere.
  • firing is performed first, followed by reduction treatment.
  • the tin-containing indium hydroxide is dehydrated to indium oxide.
  • the firing temperature is 300 to 1000 ° C.
  • a complete oxide can be obtained at 300 ° C. or higher, and intense sintering between ITO particles can be avoided at 1000 ° C. or lower.
  • a preferable firing temperature is 350 to 800 ° C. or less.
  • the firing time may be 0.1 hours or longer, but is not necessary once the dehydration reaction is completed.
  • the atmosphere is air.
  • the reduction treatment after calcination is preferably performed at a temperature of 200 to 500 ° C. in the above-described weak reducing atmosphere. If it is 200 degreeC or more, an oxygen deficiency can be provided, and if it is less than 500 degreeC, since an appropriate reduction power is obtained, insulating InO is not produced
  • the reduction treatment time is 0.5 to 5 hours. If it is less than 0.5 hours, oxygen deficiency is not sufficiently formed, and no significant change is observed even if it exceeds 5 hours. Through the above steps, an ITO powder composed of polycrystalline ITO particles can be obtained.
  • ITO powder baked with a mixed gas in which alcohol is mixed with an inert gas in this manner has many OH groups on the powder surface, a silicate ester or silane coupling agent, which will be described later, binds to the OH group. Therefore, the effect of surface treatment with a silicate ester or a silane coupling agent is higher, and an increase in the electrical resistance value of the ITO conductive film under high temperature and high humidity can be further suppressed.
  • the ITO powder is mixed so as to have a ratio of 1 to 70% by mass with respect to 100% by mass of the alcoholic solution of the dispersion medium, and stirred with a mixer to prepare an ITO conductive film forming coating material.
  • the ITO powder dispersion medium include alcohol-based solutions such as ethanol, 2-butanol, and 1-propanol.
  • the ITO powder may be added and mixed in the range of 1 to 70% by mass with respect to 100% by mass of the alcoholic solution. If the amount is less than 1% by mass, it is difficult to form a film having a sufficient thickness on the conductive film.
  • the ITO conductive film forming coating material is put in a homogenizer, a bead mill pulverizer or the like, and the ITO powder in the coating material is pulverized. Furthermore, if necessary, a binder such as silica sol gel or acrylic resin can be added to the ITO conductive film forming paint within a range not deteriorating the resistance.
  • the ITO conductive film until the surface treatment is produced, for example, as follows.
  • a base material for forming the ITO conductive film is prepared in advance.
  • This base material is a first film such as polyethylene terephthalate (PET) coated with polyurethane on one side, and the surface of the first film not coated with polyurethane is coated on a glass substrate with a double-sided adhesive tape or the like.
  • PET polyethylene terephthalate
  • an ITO conductive film forming coating material is applied to a base material fixed on a glass substrate by a bar coating method, a die coating method, a doctor blade method, or the like, and then dried.
  • the base material coated with the ITO conductive film forming coating material is peeled off from the glass substrate, and a second film such as PET is superimposed on the surface of the base material on which the ITO conductive film forming coating material is applied.
  • a second film such as PET is superimposed on the surface of the base material on which the ITO conductive film forming coating material is applied.
  • the ITO conductive film is surface-treated with a surface treatment agent.
  • a surface treatment agent composed of a silicic acid ester having four alkoxy groups having 2 or less carbon atoms or an oligomer of this silicic acid ester, or two alkoxy groups having 2 or less carbon atoms.
  • a surface treatment agent comprising a silane coupling agent having one or more alkyl groups of any one of a long-chain alkyl group or an alkyl group partially substituted with fluorine is used.
  • R, R 1 and R 2 are each an alkyl group.
  • the surface treatment agent comprising the silicate ester or the silicate ester oligomer a structure in which a silicate ester or a silicate hydrolyzate is bonded to the surface of the polycrystalline ITO conductive film is obtained.
  • the surface treatment agent comprising the silane coupling agent
  • Or sianol group generated by hydrolysis of alkoxy group
  • the bonding configuration between the hydroxyl group on the surface of the polycrystalline ITO conductive film and the surface treatment agent is via —OH on the surface of the ITO conductive film.
  • Examples of the silicic acid ester having four alkoxy groups having 2 or less carbon atoms include tetramethoxysilane (carbon number 1) or tetraethoxysilane (carbon number 2). Examples are silane (carbon number 1) trimer to pentamer or tetraethoxysilane (carbon number 2) trimer to pentamer.
  • a silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups having an amino group or a mercapto group as a terminal group includes N-2- (aminoethyl) Examples are -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, or 3-mercaptopropyltrimethoxysilane.
  • silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more long-chain alkyl groups having 6 or more carbon atoms
  • examples of the silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more long-chain alkyl groups having 6 or more carbon atoms include hexyltrimethoxysilane and hexyltriethoxysilane. Or decyltrimethoxysilane is illustrated.
  • trifluoropropyltrimethoxysilane is exemplified as the silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups partially substituted with fluorine.
  • the silicate ester of the present invention preferably has a plurality of ester bonds that can easily form a network as SiO 2 after being bonded to the surface of the ITO particles.
  • ⁇ Surface Treatment Method for ITO Conductive Film (Method for Producing ITO Conductive Film Including Surface Treatment)>
  • a surface treatment solution is prepared by dissolving the surface treatment agent in a solvent so that the concentration of the surface treatment agent is 10 to 100% by mass.
  • a solvent alcohol, ketone, water, or a mixed solvent containing these can be used.
  • a surface treatment agent is included in the nitrogen gas by bubbling nitrogen gas preheated to 20 to 150 ° C. in the surface treatment liquid.
  • the ITO film produced by the above method By placing the ITO film produced by the above method in a glass container having an internal volume of 5 L and circulating a gas containing the surface treatment agent vapor at 0.1 to 5 L / min for 1 to 180 minutes, Surface treatment of ITO film is performed. If the concentration of the surface treatment agent, the gas flow rate, the circulation time, and the gas temperature are less than the above lower limit values, sufficient surface treatment effect cannot be obtained. The liquid tends to condense on the ITO film surface, which is not preferable.
  • a spin coating method and a dip coating method will be described as representative examples of the coating method.
  • a surface treatment solution is prepared by dissolving the surface treatment agent in a solvent so that the concentration of the surface treatment agent is 0.1 to 10% by mass.
  • a solvent alcohol, ketone, water, or a mixed solvent containing these can be used.
  • the ITO film produced by the above method is horizontally disposed and rotated, and the surface treatment liquid is dropped onto the surface of the ITO film to perform surface treatment of the ITO film.
  • the rotation speed of the spout is preferably 100 to 5000 rpm, but is not limited to this range as long as the film does not cause unevenness.
  • a surface treatment solution is prepared by dissolving the surface treatment agent in a solvent so that the concentration of the surface treatment agent is 0.01 to 10% by mass.
  • a solvent alcohol, ketone, water, or a mixed solvent containing these can be used.
  • the ITO film produced by the above method is immersed (dipped) in this surface treatment solution for 0.1 to 60 minutes, and then dried to perform surface treatment of the ITO film.
  • concentration of the surface treatment agent is less than the above lower limit value, the surface treatment effect cannot be sufficiently obtained, and when the concentration exceeds the above upper limit value, an excessive surface treatment liquid remains on the film, thereby causing uneven treatment on the ITO film. Therefore, it is not preferable.
  • the coating method is not limited to the spin coating method and the dip coating method, and other coating methods can be used in the present invention.
  • the ITO powder thus obtained is added and mixed so that the ratio is 25% by mass with respect to the dispersion medium, and is stirred and dispersed with an ultrasonic homogenizer for 30 minutes to prepare a coating for forming an ITO conductive film.
  • This ITO conductive film forming coating is formed on a PET film by a bar coating method in accordance with the method for producing a transparent conductive film described above, and pressure is applied to this film at a roll pressure of 700 kg / cm and a delivery speed of 30 cm / min. Thus, an ITO conductive film formed on the PET film was obtained.
  • the ITO conductive film thus obtained was cut into a size of 5 cm ⁇ 5 cm and surface-treated with the above-described treatment method using the surface treatment agent shown in Table 1.
  • the ITO film produced by the above method is put in a glass container, and the gas containing the vapor of the surface treatment agent is circulated at 0.5 L / min for 60 minutes. Was done.
  • This gas is obtained by bubbling a preheated nitrogen gas at 80 ° C. in a surface treatment liquid so that the surface treatment agent is included in the nitrogen gas.
  • the ITO conductive film surface-treated with a surface treatment agent comprising a silicate ester having four alkoxy groups having 2 or less carbon atoms or a surface treatment agent comprising an oligomer of these silicate esters is obtained after humidification. It has been found that the increase in the electric resistance value can be sufficiently suppressed even when the electric resistance value is relatively low and the temperature and humidity are high.
  • Examples 5 and 6 of the ITO conductive film surface-treated with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane having an amino group as a terminal group and 3-aminopropyltrimethoxysilane The electric resistance values after humidification were reduced to 823 ⁇ / sq and 602 ⁇ / sq, and the rate of change from the initial electric resistance value to the electric resistance value after humidification was reduced to 2.6 times and 2.1 times.
  • the electric resistance values after humidification were 739 ⁇ / sq and 624 ⁇ . / Sq, and the rate of change from the initial electrical resistance value to the electrical resistance value after humidification was reduced to 2.3 times and 1.8 times.
  • the surface treatment is performed by the surface treatment agent comprising a silane coupling agent having at least two alkoxy groups having 2 or less carbon atoms and at least one alkyl group having an amino group or a mercapto group as a terminal group. It has been found that the ITO conductive film has a relatively low electrical resistance value after humidification and can sufficiently suppress an increase in the electrical resistance value even under high temperature and high humidity.
  • Examples 10, 11 and 12 of the ITO conductive film surface-treated with hexyltrimethoxysilane, decyltrimethoxysilane and hexyltriethoxysilane having a long-chain alkyl group having 6 or more carbon atoms humidification was performed.
  • the post-electric resistance value decreased to 1025 to 1473 ⁇ / sq, and the rate of change from the initial electric resistance value to the post-humidified electric resistance value decreased to 3.1 to 4.5 times.
  • the surface treatment is performed by the surface treatment agent comprising a silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more long-chain alkyl groups having 6 or more carbon atoms. It has been found that the ITO conductive film has a relatively low electrical resistance value after humidification and can sufficiently suppress an increase in the electrical resistance value even under high temperature and high humidity.
  • Example 9 in which the ITO conductive film was formed using ITO powder surface-treated with trifluoropropyltrimethoxysilane having an alkyl group partially substituted with fluorine, The electrical resistance value was reduced to 964 ⁇ / sq, and the rate of change from the initial electrical resistance value to the electrical resistance value after humidification was reduced to 3.5 times.
  • ITO surface-treated with a surface treatment agent comprising a silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups partially substituted with fluorine. It has been found that the conductive film has a relatively low electrical resistance value after humidification and can sufficiently suppress an increase in the electrical resistance value even under high temperature and high humidity.

Abstract

This ITO conductive film is surface-treated with a surface treatment agent that is composed of a silicic acid ester having four alkoxy groups with two or less carbon atoms or an oligomer of this silicic acid ester, or alternatively surface-treated with a surface treatment agent that is composed of a silane coupling agent having two or more alkoxy groups with two or less carbon atoms and one or more alkyl groups that are selected from among alkyl groups having a terminal amino group or a terminal mercapto group, long-chain alkyl groups having six or more carbon atoms and alkyl groups partially substituted by a fluorine atom.

Description

表面処理されたＩＴＯ導電膜及びその製造方法Surface-treated ITO conductive film and method for producing the same
　本発明は、高温高湿下において電気抵抗値の上昇を抑制し得る表面処理されたＩＴＯ導電膜及びその製造方法に関する。本明細書において、ＩＴＯとはインジウム錫酸化物(Indium Tin Oxide)をいう。
　本願は、２０１３年９月３０日に、日本に出願された特願２０１３－２０５１４０号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a surface-treated ITO conductive film capable of suppressing an increase in electric resistance value under high temperature and high humidity and a method for producing the same. In this specification, ITO refers to indium tin oxide.
This application claims priority based on Japanese Patent Application No. 2013-205140 filed in Japan on September 30, 2013, the contents of which are incorporated herein by reference.
　ＬＣＤ(Liquid Crystal Display)やＰＤＰ(Plasma Display Panel)、有機ＥＬ(ElectroLuminescence)、タッチパネル等の表示装置には、透明電極が用いられている。この透明電極は、ＩＴＯ等からなる透明導電材料によって構成されることが多い。このような透明電極は、通常スパッタリング法などで膜状に形成される（例えば、特許文献１参照）。しかしながらスパッタリング装置は高価であり、かつ、成膜の効率が悪く、また、その膜はひび割れし易い等の問題がある。このひび割れの起こりにくい屈曲性に優れたＩＴＯ導電膜を形成する方法として、スパッタリング法に代わって、ＩＴＯ導電膜形成用塗料を基板に塗布する方法が提案されている。しかしながら、塗布方式で得られた透明電極は、高温高湿下におかれると、雰囲気中の酸素や水分に起因して電気抵抗値が上昇する傾向にあり、これが信頼性を低下させる一因となっていた。 Transparent electrodes are used in display devices such as LCD (Liquid Crystal Display), PDP (Plasma Display Panel), organic EL (ElectroLuminescence), and touch panel. This transparent electrode is often composed of a transparent conductive material made of ITO or the like. Such a transparent electrode is usually formed into a film by a sputtering method or the like (see, for example, Patent Document 1). However, the sputtering apparatus is expensive and has a problem that the film formation efficiency is low and the film is easily cracked. As a method of forming an ITO conductive film excellent in flexibility, which is less prone to cracking, a method of applying an ITO conductive film forming coating to a substrate instead of the sputtering method has been proposed. However, when the transparent electrode obtained by the coating method is placed under high temperature and high humidity, the electrical resistance value tends to increase due to oxygen and moisture in the atmosphere. It was.
　この問題を解決するために、塗布方式によるＩＴＯ導電膜形成用塗料として、耐水性を有するＩＴＯ粉末のような導電粉の表面を表面処理剤で処理してなる表面処理導電粉と硬化性化合物を含む透明導電材料（例えば、特許文献２参照）や、樹脂とＩＴＯ粉末のような透明導電粒子とシリカ材料とシランカップリング剤とを含有する透明導電材料（例えば、特許文献３参照）が提案されている。 In order to solve this problem, as a coating for forming an ITO conductive film by a coating method, a surface-treated conductive powder and a curable compound obtained by treating the surface of a conductive powder such as ITO powder having water resistance with a surface treatment agent Transparent conductive materials (for example, see Patent Document 2), transparent conductive materials containing transparent conductive particles such as resin, ITO powder, silica material, and silane coupling agent (for example, see Patent Document 3) have been proposed. ing.
特開２００４－３１５９５１号公報（段落［０００２］）JP 2004-315951 A (paragraph [0002]) 特開２００６－５９７７２号公報（要約、請求項１）JP 2006-59772 A (summary, claim 1) 特開２００９－１３５０４４号公報（要約、請求項１）JP 2009-135044 (Abstract, Claim 1)
　上記特許文献２及び３に示される透明導電材料により形成されたＩＴＯ導電膜の透明電極は、高温高湿下であっても水分の影響による電気抵抗値の上昇を抑制することが可能である。
　ここで示す従来の高温高湿下とは、例えば、温度６０℃、湿度９５％ＲＨ、７５０時間等である。
　しかしながら、近年では、透明電極の用途が一層多岐にわたっており、従来にも増して厳しい条件下であっても、高温高湿下における透明電極の電気抵抗値の上昇を抑制できるＩＴＯ導電膜が求められている。 The transparent electrode of the ITO conductive film formed of the transparent conductive material disclosed in Patent Documents 2 and 3 can suppress an increase in electrical resistance value due to the influence of moisture even under high temperature and high humidity.
The conventional high temperature and high humidity shown here is, for example, a temperature of 60 ° C., a humidity of 95% RH, and 750 hours.
However, in recent years, the use of transparent electrodes has become more diverse, and there has been a demand for an ITO conductive film that can suppress an increase in the electrical resistance value of a transparent electrode under high temperature and high humidity even under severer conditions than before. ing.
　本発明の目的は、従来にも増して厳しい条件下であっても、高温高湿下における電気抵抗値の上昇を抑制可能な透明電極である表面処理されたＩＴＯ導電膜及びその製造方法を提供することにある。 An object of the present invention is to provide a surface-treated ITO conductive film which is a transparent electrode capable of suppressing an increase in electrical resistance value under high temperature and high humidity even under severer conditions than before, and a method for producing the same There is to do.
　本発明の第１の観点は、炭素数が２以下であるアルコキシ基を４つ有する珪酸エステル又はこの珪酸エステルのオリゴマー体からなる表面処理剤により、或いは炭素数が２以下であるアルコキシ基を２つ以上有し、かつアミノ基若しくはメルカプト基を末端基に有するアルキル基、炭素数が６以上である長鎖のアルキル基、又は一部がフッ素で置換されたアルキル基のいずれか１種のアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤により、表面処理されたＩＴＯ導電膜である。 According to a first aspect of the present invention, a surface treatment agent comprising a silicate ester having 4 alkoxy groups having 2 or less carbon atoms or an oligomer of the silicate ester, or 2 alkoxy groups having 2 or less carbon atoms. An alkyl group having at least one amino group or mercapto group as a terminal group, a long-chain alkyl group having 6 or more carbon atoms, or an alkyl group partially substituted with fluorine. It is an ITO conductive film surface-treated with a surface treatment agent comprising a silane coupling agent having one or more groups.
　本発明の第２の観点は、第１の観点に基づく発明であって、更に珪酸エステルが、炭素数が１のアルキル基を有するテトラメトキシシラン、又は炭素数が２のアルキル基を有するテトラエトキシシランである。 A second aspect of the present invention is the invention based on the first aspect, wherein the silicate ester further comprises tetramethoxysilane having an alkyl group having 1 carbon atom or tetraethoxy having an alkyl group having 2 carbon atoms. Silane.
　本発明の第３の観点は、第１の観点に基づく発明であって、更にシランカップリング剤が、Ｎ－２－(アミノエチル)－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、及びデシルトリメトキシシランからなる群より選択される何れか一つである。 A third aspect of the present invention is the invention based on the first aspect, wherein the silane coupling agent is N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxy. Any one selected from the group consisting of silane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and decyltrimethoxysilane. One.
　本発明の第４の観点は、第１ないし第３の観点のいずれか１つの観点に基づく表面処理剤を溶剤に溶解した表面処理液の蒸気を容器に入れたＩＴＯ導電膜に気相暴露することによりＩＴＯ導電膜の表面を処理するＩＴＯ導電膜の製造方法であることを特徴とする。 According to a fourth aspect of the present invention, a vapor of a surface treatment solution in which a surface treatment agent based on any one of the first to third aspects is dissolved in a solvent is exposed in a vapor phase to an ITO conductive film in a container. This is a method for producing an ITO conductive film in which the surface of the ITO conductive film is treated.
　本発明の第５の観点は、第１ないし第３の観点のいずれか１つの観点に基づく表面処理剤を溶剤に溶解した表面処理液をＩＴＯ導電膜の表面に塗布することによりＩＴＯ導電膜の表面を処理するＩＴＯ導電膜の製造方法であることを特徴とする。 According to a fifth aspect of the present invention, there is provided an ITO conductive film by applying a surface treatment solution obtained by dissolving a surface treatment agent based on any one of the first to third aspects in a solvent to the surface of the ITO conductive film. It is a manufacturing method of the ITO electrically conductive film which processes the surface, It is characterized by the above-mentioned.
　本発明の第６の観点は、第５の観点に基づく発明であって、前記表面処理液のＩＴＯ導電膜の表面への塗布がスピンコート法又はディップコート法により行われるＩＴＯ導電膜の製造方法である。 A sixth aspect of the present invention is an invention based on the fifth aspect, wherein the surface treatment liquid is applied to the surface of the ITO conductive film by a spin coat method or a dip coat method. It is.
　元来、ＩＴＯの主たる構成要素であるＩｎ２Ｏ３は、Bixbyite構造をなし、蛍石構造から規則的に酸素が抜けた構造と表現できる。この構造はドーパントであるＳｎの量が増えるなどすると、格子間に酸素を取り込みやすい構造になっている。このためＩＴＯ導電膜が高温高湿下におかれると、導電膜表面に吸着した水が導電膜を構成するＩＴＯ粉末表面の酸素空孔や格子間に、－ＯＨとして結合し、キャリア電子をトラップすることから、ＩＴＯ導電膜の導電性を低下させる。 Originally, the main component of ITO, In 2 O 3, has a Bixbyite structure, and can be expressed as a structure in which oxygen is regularly removed from the fluorite structure. This structure has a structure in which oxygen is easily taken in between lattices when the amount of Sn as a dopant is increased. For this reason, when the ITO conductive film is placed under high temperature and high humidity, water adsorbed on the surface of the conductive film is bonded as —OH between oxygen vacancies and lattices on the surface of the ITO powder constituting the conductive film, and traps carrier electrons. Therefore, the conductivity of the ITO conductive film is reduced.
　本発明の第１の観点のＩＴＯ導電膜は、上述した特定の表面処理剤で処理される。表面処理剤が上記珪酸エステルの場合には、上記導電膜を構成するＩＴＯ粉末表面の酸素空孔や格子間に珪酸エステルが結合することで、水に対する安定性が大幅に改善されると考えられる。また上記シランカップリング剤の場合には、上記導電膜を構成するＩＴＯ粉末表面の酸素空孔や格子間にアミノ基若しくはメルカプト基などが結合することで、水に対する安定性が大幅に改善されると考えられる。また、ＩＴＯの表面には、既に粒子表面に－ＯＨが存在する。即ち、ＩＴＯ導電膜を構成する多結晶ＩＴＯ粒子表面に－ＯＨが存在する。この－ＯＨに上記珪酸エステル又は上記シランカップリング剤が結合することによって、トラップされた電子が開放され、導電性が向上する効果も得られる。この結果、本発明の導電膜は、高温高湿下における電気抵抗値の上昇を抑制することができる。 The ITO conductive film according to the first aspect of the present invention is treated with the specific surface treatment agent described above. When the surface treatment agent is the silicate ester, it is considered that the stability to water is greatly improved by bonding the silicate ester between oxygen vacancies and lattices on the surface of the ITO powder constituting the conductive film. . In the case of the silane coupling agent, the stability to water is greatly improved by bonding an amino group or a mercapto group between oxygen vacancies or lattices on the surface of the ITO powder constituting the conductive film. it is conceivable that. Further, on the surface of ITO, —OH already exists on the particle surface. That is, —OH exists on the surface of the polycrystalline ITO particles constituting the ITO conductive film. By bonding the silicate ester or the silane coupling agent to this —OH, the trapped electrons are released, and the effect of improving the conductivity is also obtained. As a result, the conductive film of the present invention can suppress an increase in electrical resistance value under high temperature and high humidity.
　本発明の第２の観点のＩＴＯ導電膜では、珪酸エステルとして、炭素数が１のアルキル基を有するテトラメトキシシラン、又は炭素数が２のアルキル基を有するテトラエトキシシランを選択する。これら珪酸エステルは、炭素数が小さいため、反応性が高くなる。この結果、珪酸エステルがＩＴＯ表面に結合しやすい効果がある。 In the ITO conductive film according to the second aspect of the present invention, tetramethoxysilane having an alkyl group having 1 carbon atom or tetraethoxysilane having an alkyl group having 2 carbon atoms is selected as the silicate ester. Since these silicate esters have a small number of carbon atoms, the reactivity increases. As a result, there is an effect that the silicate ester is easily bonded to the ITO surface.
　本発明の第３の観点のＩＴＯ導電膜では、シランカップリング剤として、Ｎ－２－(アミノエチル)－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、及びデシルトリメトキシシランからなる群より選択される何れか一つを選択する。これらのシランカップリング剤は、末端基の持つ立体障害や極性のため、ＩＴＯ表面にＨ２Ｏが接近することを阻害する効果がある。 In the ITO conductive film according to the third aspect of the present invention, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxy are used as silane coupling agents. Any one selected from the group consisting of silane, 3-mercaptopropyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and decyltrimethoxysilane is selected. These silane coupling agents have an effect of inhibiting H 2 O from approaching the ITO surface because of the steric hindrance and polarity of the end groups.
本発明のＩＴＯ粉末の多結晶ＩＴＯ粒子の模式斜視図である。It is a model perspective view of the polycrystalline ITO particle | grains of the ITO powder of this invention. 本発明のＩＴＯ粉末の多結晶ＩＴＯ粒子の模式断面図である。It is a schematic cross section of the polycrystalline ITO particles of the ITO powder of the present invention. 本発明の多結晶ＩＴＯ粒子、ＩＴＯ粉末の一形態をＴＥＭによって撮像した１００００倍の写真図である。It is a 10,000 times photograph figure which imaged one form of the polycrystalline ITO particle of the present invention, and ITO powder by TEM. 本発明の多結晶ＩＴＯ粒子、ＩＴＯ粉末の一形態をＴＥＭによって撮像した５００００倍の写真図である。It is a 50000 times photograph figure which imaged one form of the polycrystalline ITO particle of the present invention, and ITO powder by TEM.
　次に本発明を実施するための形態を図面に基づいて説明する。 Next, modes for carrying out the present invention will be described with reference to the drawings.
　＜ＩＴＯ粉末＞
　図１Ａ及び図１Ｂに、本発明のＩＴＯ導電膜を形成するための材料であるＩＴＯ粉末の一例を示す。本発明のＩＴＯ導電膜はこのＩＴＯ粉末によらず、他の方法で製造されるＩＴＯ粉末により形成することができる。図１Ａ及び図１Ｂに模式的に示されているように、このＩＴＯ粉末は、多結晶ＩＴＯ粒子１０からなる。多結晶ＩＴＯ粒子１０は、棒状中心核１１と複数の棒状体１２からなり、棒状中心核１１の長手方向に基本的に同じ向きに沿って棒状中心核１１を囲むようにして棒状体１２と一体的に形成されている。更に図２Ａ及び図２Ｂの写真図に示すように、多結晶ＩＴＯ粒子では、複数の短い棒状体が小枝のように観察され、これらの短い棒状体が棒状中心核の周囲を囲みながら互いに隣接し合いながら同様の方向に並んで棒状中心核に固着していることが観察される。なお、図２Ａ及び図２Ｂに示すように複数の棒状体のそれぞれの径及び長さは必ずしも同一である必要はなく、その断面形状、表面形状も必ずしも同一である必要はない。 <ITO powder>
1A and 1B show an example of ITO powder that is a material for forming the ITO conductive film of the present invention. The ITO conductive film of the present invention can be formed of ITO powder produced by other methods without using this ITO powder. As schematically shown in FIGS. 1A and 1B, the ITO powder is composed of polycrystalline ITO particles 10. The polycrystalline ITO particles 10 are composed of a rod-shaped central core 11 and a plurality of rod-shaped bodies 12, and are integrally formed with the rod-shaped body 12 so as to surround the rod-shaped central core 11 along the same direction in the longitudinal direction of the rod-shaped central core 11. Is formed. 2A and 2B, in the polycrystalline ITO particles, a plurality of short rods are observed as twigs, and these short rods are adjacent to each other while surrounding the rod-shaped central core. It is observed that they stick to the rod-shaped central core side by side in the same direction. As shown in FIGS. 2A and 2B, the diameters and lengths of the plurality of rod-shaped bodies are not necessarily the same, and the cross-sectional shape and the surface shape are not necessarily the same.
　図１Ａで示される、上記多結晶ＩＴＯ粒子１０の棒状中心核１２の長手方向の平均長さＬは、０．２～５．０μｍ、好ましくは１．０～５．０μｍの範囲にある。図１Ａ及び図１Ｂで示される、多結晶ＩＴＯ粒子１０の前記長手方向に対して垂直な方向の断面における平均直径をＤとするとき、Ｌ／Ｄが２～２０、好ましくは３～１０の範囲にある。Ｌは０．２μｍ未満では、ＩＴＯ導電膜を形成する基板面に対して垂直に立ち易くなり、ラグビーボールのように倒れやすい効果が得られない。Ｌが５．０μｍを越えると、粒子同士のパッキングが悪くなる。またＬ／Ｄが２未満では異方性による導電性向上の効果が得られず、２０を越えると塗膜作製時に棒状粒子が破断し、短くなってしまうという不具合を生じる。 1A, the average length L in the longitudinal direction of the rod-shaped central core 12 of the polycrystalline ITO particle 10 is in the range of 0.2 to 5.0 μm, preferably 1.0 to 5.0 μm. When the average diameter in the cross section perpendicular to the longitudinal direction of the polycrystalline ITO particles 10 shown in FIGS. 1A and 1B is D, L / D is in the range of 2 to 20, preferably 3 to 10. It is in. When L is less than 0.2 μm, it becomes easy to stand perpendicular to the substrate surface on which the ITO conductive film is formed, and the effect of being easily overturned like a rugby ball cannot be obtained. When L exceeds 5.0 μm, the packing between the particles is deteriorated. If L / D is less than 2, the effect of improving conductivity due to anisotropy cannot be obtained. If L / D is more than 20, the rod-like particles are broken and shortened when the coating film is produced.
　上記多結晶ＩＴＯ粒子は、上記の形状を持つため、例えば上記多結晶ＩＴＯ粒子を用いて塗布型ＩＴＯフィルムを製造すると、樹脂フィルムに当該ＩＴＯ粉末を含む塗料を塗布したときや、前記塗料の塗布面を加圧したときに、多結晶ＩＴＯ粒子が塗布方向に沿って樹脂フィルム面に配向し易い。即ち、上記多結晶ＩＴＯ粒子は樹脂フィルム面に転がって横たわり易い。また、上記ＩＴＯ粒子は多結晶であるため、粒界で適度なずれが生じる。その結果、粒子間の空隙が充填され易くなり、多結晶ＩＴＯ粒子間が密になる。従って、上記ＩＴＯ粒子を用いて透明電極である導電膜を形成したときに、より導電膜の電気抵抗を下げ、良好な導電性が得られる。またそればかりでなく、多結晶ＩＴＯ粒子間が充填される結果、当該ＩＴＯ粉末を含む塗料を透明基板やフィルム上に塗布したとき塗布層が緻密組織になり、これにより薄膜太陽電池の受光面やオプティカルデバイスの透明電極である導電膜の光透過率を良好とし、かつヘーズを低下させることができる。 Since the polycrystalline ITO particles have the above-mentioned shape, for example, when a coated ITO film is produced using the polycrystalline ITO particles, when the paint containing the ITO powder is applied to a resin film, or when the paint is applied When the surface is pressurized, the polycrystalline ITO particles are easily oriented on the resin film surface along the coating direction. That is, the polycrystalline ITO particles are easy to roll and lie on the resin film surface. Further, since the ITO particles are polycrystalline, an appropriate shift occurs at the grain boundaries. As a result, voids between the particles are easily filled, and the polycrystalline ITO particles are dense. Therefore, when the conductive film which is a transparent electrode is formed using the ITO particles, the electrical resistance of the conductive film is further lowered and good conductivity is obtained. In addition, as a result of filling the space between the polycrystalline ITO particles, when the paint containing the ITO powder is applied on a transparent substrate or film, the coating layer becomes a dense structure. The light transmittance of the conductive film which is a transparent electrode of the optical device can be improved, and haze can be reduced.
　＜ＩＴＯ粉末の製造方法＞
　先ず、第１の工程として、スズ塩とインジウム塩とを所定の割合で秤量混合し、当該混合物を純水に溶解してスズ塩とインジウム塩との混合溶液とし、当該混合溶液とアルカリとを反応させて、スズ含有水酸化インジウムの懸濁液を生成させる。混合の方法としては、スズ塩とインジウム塩との混合水溶液へ、アンモニア等のアルカリを添加して反応させる方法が好ましい。スズ塩とインジウム塩との混合水溶液へ、アルカリを添加すると、異方性粒子が生成し易い上に、アルカリ添加の際の温度、添加速度及び／又は粒子濃度を制御することによって、生成する水酸化物粒子の大きさや軸比を制御できる。 <Production method of ITO powder>
First, as a first step, a tin salt and an indium salt are weighed and mixed at a predetermined ratio, the mixture is dissolved in pure water to obtain a mixed solution of a tin salt and an indium salt, and the mixed solution and an alkali are mixed. React to produce a suspension of tin-containing indium hydroxide. As a mixing method, a method of adding an alkali such as ammonia to a mixed aqueous solution of a tin salt and an indium salt and reacting them is preferable. When an alkali is added to a mixed aqueous solution of a tin salt and an indium salt, anisotropic particles are likely to be generated, and the generated water is controlled by controlling the temperature, the addition rate and / or the particle concentration during the addition of the alkali. The size and axial ratio of the oxide particles can be controlled.
　更に、この実施の形態では、所定周波数の超音波を混合中の上記反応液に照射する。この超音波の付与により、ＩＴＯ棒状中心核の周囲にこのＩＴＯ棒状中心核より短い複数のＩＴＯ棒状体が、ＩＴＯ棒状中心核の長手方向と同様の向きに沿いかつＩＴＯ棒状中心核を囲むように一体的に形成された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を製造することができる。超音波の周波数は２０～１００００ｋＨｚとする。周波数が、２０ｋＨｚ未満では超音波の攪拌効果が弱く、一方、１００００ｋＨｚを越えると超音波の出力が落ちて、十分な効果が得られない。周波数は更に２０～１０００ｋＨｚとすることが好ましい。 Furthermore, in this embodiment, the reaction liquid being mixed is irradiated with ultrasonic waves having a predetermined frequency. By applying this ultrasonic wave, a plurality of ITO rods shorter than the ITO rod-shaped central core are arranged around the ITO rod-shaped central core along the same direction as the longitudinal direction of the ITO rod-shaped central core and surround the ITO rod-shaped central core. An ITO powder composed of integrally formed polycrystalline ITO particles can be produced. The frequency of the ultrasonic wave is 20 to 10,000 kHz. If the frequency is less than 20 kHz, the ultrasonic stirring effect is weak. On the other hand, if it exceeds 10,000 kHz, the output of the ultrasonic wave is lowered and a sufficient effect cannot be obtained. The frequency is further preferably 20 to 1000 kHz.
　超音波を上記の懸濁液に付与する所定時間は、周波数や中和液の容量等によって適宜調整する必要がある。例えば、超音波の周波数が１００ｋＨｚのときで、反応液の容量が１Ｌのときには超音波を照射しながら、アルカリを滴下する時間は、２０～６００分が好ましい。超音波の付与時間は短すぎると、超音波照射の効果が十分に得られない不具合があり、長すぎると、粒子が長くなりすぎる不具合がある。超音波が反応液に均一に付与されるように、反応液の液面は超音波照射装置の液面（照射装置から反応器へ超音波を伝える媒体）と同一になるようにする。この超音波の付与によって、異方性ＩＴＯ粒子の単体同士の凝集を防ぐと同時に、ＩＴＯ棒状中心核の周囲に中心核より短い複数のＩＴＯ棒状体が、ＩＴＯ棒状中心核の長手方向と同様の向きに沿いかつＩＴＯ棒状中心核を囲むように固着された多結晶ＩＴＯ粒子を得ることができる。 It is necessary to appropriately adjust the predetermined time for applying the ultrasonic wave to the suspension according to the frequency, the volume of the neutralizing solution, and the like. For example, when the frequency of the ultrasonic wave is 100 kHz and the volume of the reaction solution is 1 L, the time for dropping the alkali while irradiating the ultrasonic wave is preferably 20 to 600 minutes. If the application time of the ultrasonic wave is too short, there is a problem that the effect of ultrasonic irradiation cannot be sufficiently obtained, and if it is too long, there is a problem that the particles become too long. The liquid level of the reaction liquid is set to be the same as the liquid level of the ultrasonic irradiation apparatus (medium for transmitting ultrasonic waves from the irradiation apparatus to the reactor) so that the ultrasonic waves are uniformly applied to the reaction liquid. By applying this ultrasonic wave, agglomeration of single pieces of anisotropic ITO particles is prevented, and at the same time, a plurality of ITO rods shorter than the central core around the ITO rod central core are the same as the longitudinal direction of the ITO rod central core. Polycrystalline ITO particles fixed along the direction and surrounding the ITO rod-like central core can be obtained.
　ここで、スズ及びインジウムの塩としては、塩酸塩、硫酸塩、又は硝酸塩などがあるが、一般的には塩酸塩が好ましい。また、アルカリとしては、アンモニア、苛性ソーダ、苛性カリ、又はそれらの炭酸塩が用いられるが、スズ含有水酸化インジウムのスラリー生成後における不純物を削減する観点からアンモニアを用いることが好ましい。 Here, as the salt of tin and indium, there are hydrochloride, sulfate, nitrate, etc., but hydrochloride is generally preferable. As the alkali, ammonia, caustic soda, caustic potash, or a carbonate thereof is used, but ammonia is preferably used from the viewpoint of reducing impurities after the slurry formation of tin-containing indium hydroxide.
　生成したスズ含有水酸化インジウムのスラリーを前記懸濁液の固液分離により採集し、純水により不純物を洗浄することで、純度を高めたスズ含有水酸化インジウムのケーキが得られる。得られたケーキを、室温以上、望ましくは８０℃以上の温度で乾燥することにより、スズ含有水酸化インジウムの乾燥粉が得られる。 The produced tin-containing indium hydroxide slurry is collected by solid-liquid separation of the suspension, and the impurities are washed with pure water to obtain a tin-containing indium hydroxide cake with increased purity. The obtained cake is dried at a temperature of room temperature or higher, preferably 80 ° C. or higher, whereby a dry powder of tin-containing indium hydroxide is obtained.
　スズ含有水酸化インジウム中において、スズは水酸化インジウムのインジウムと置換している場合もあるが、酸化スズ及び／又は水酸化スズとして水酸化インジウムと共沈している場合もあり、酸化スズ及び／又は水酸化スズとして水酸化インジウムと非晶質の混合体となっている場合もある。 In tin-containing indium hydroxide, tin may be substituted for indium in indium hydroxide, but may be co-precipitated with indium hydroxide as tin oxide and / or tin hydroxide. In some cases, the mixture is in the form of indium hydroxide and amorphous as tin hydroxide.
　上述したように、スズ含有水酸化インジウムの粒子径は、水酸化物を得る工程で決定される。具体的には、反応温度を４０～９０℃の範囲に、反応時間（全中和にかかる時間）を２０～６００分の範囲に、最終粒子濃度を０．０１～３ｍｏｌ／リットルの範囲にそれぞれ制御することで所望の粒径を有するスズ含有水酸化インジウムを得ることができる。 As described above, the particle diameter of the tin-containing indium hydroxide is determined in the step of obtaining a hydroxide. Specifically, the reaction temperature is in the range of 40 to 90 ° C., the reaction time (total neutralization time) is in the range of 20 to 600 minutes, and the final particle concentration is in the range of 0.01 to 3 mol / liter. By controlling, tin-containing indium hydroxide having a desired particle size can be obtained.
　ここで、例えば多結晶ＩＴＯ粒子の平均長さＬが１μｍ、平均直径Ｄが０．２μｍであるスズ含有水酸化インジウムの針状粒子を合成する場合には、反応温度を６０℃、反応時間（全中和にかかる時間）を７５分、最終粒子濃度を０．５ｍｏｌ／リットルとすれば良い。一方、上記スズ含有水酸化インジウムの針状粒子より平均長さの小さな粒子を製造する場合は、反応温度を低く設定するか、反応速度を短くするか又は粒子濃度を高くすればよい。なお、最終的に生成される多結晶ＩＴＯ粒子のサイズは、当該スズ含有水酸化物のサイズによりほぼ決定される。即ち、当該スズ含有水酸化物はＩＴＯ粒子へ変化する際、平均長さＬ及び平均直径Ｄ共に７０～８０％程度収縮する。 Here, for example, when synthesizing needle-like particles of tin-containing indium hydroxide having an average length L of polycrystalline ITO particles of 1 μm and an average diameter D of 0.2 μm, the reaction temperature is 60 ° C., the reaction time ( The time required for total neutralization) may be 75 minutes, and the final particle concentration may be 0.5 mol / liter. On the other hand, when producing particles having an average length smaller than the needle-like particles of tin-containing indium hydroxide, the reaction temperature may be set low, the reaction rate may be shortened, or the particle concentration may be increased. Note that the size of the finally produced polycrystalline ITO particles is substantially determined by the size of the tin-containing hydroxide. That is, when the tin-containing hydroxide changes to ITO particles, both the average length L and the average diameter D shrink about 70 to 80%.
　次に、第２の工程である、得られたスズ含有水酸化インジウムを焼成する工程について説明する。この焼成工程の目的は、スズ含有水酸化インジウムから、酸化物であるＩＴＯを生成させること及び得られるＩＴＯの結晶に酸素欠損を与えることである。従って、この焼成工程はＩＴＯの結晶に酸素欠損を与えるために不活性ガスと還元性ガスとを混合した弱還元雰囲気下で行われる。通常、弱還元雰囲気として、窒素やヘリウム、アルゴン等の不活性ガスに、水素や一酸化炭素、アンモニアガス、アルコールを混合した混合ガスが用いられる。混合ガスにおける各ガスの混合比率はＩＴＯの結晶に付与しようとする酸素欠損量により適宜決定される。但し混合ガスの還元力が強すぎると、スズ含有水酸化インジウムはＩｎＯ、金属Ｉｎ等になってしまう。また、水素や一酸化炭素等の混合比率は、混合ガスが大気中で爆発限界を越えない程度の濃度にすることが望ましい。 Next, the step of firing the obtained tin-containing indium hydroxide, which is the second step, will be described. The purpose of this firing step is to generate ITO as an oxide from tin-containing indium hydroxide and to give oxygen deficiency to the resulting ITO crystals. Therefore, this firing step is performed in a weak reducing atmosphere in which an inert gas and a reducing gas are mixed to give oxygen deficiency to the ITO crystal. Usually, as a weak reducing atmosphere, a mixed gas in which hydrogen, carbon monoxide, ammonia gas, or alcohol is mixed with an inert gas such as nitrogen, helium, or argon is used. The mixing ratio of each gas in the mixed gas is appropriately determined by the amount of oxygen deficiency to be imparted to the ITO crystal. However, if the reducing power of the mixed gas is too strong, the tin-containing indium hydroxide becomes InO, metal In, or the like. In addition, the mixing ratio of hydrogen, carbon monoxide, or the like is desirably set to such a concentration that the mixed gas does not exceed the explosion limit in the atmosphere.
　焼成工程では、初めに焼成が行われ、続いて還元処理が行われる。焼成では、スズ含有水酸化インジウムを脱水して酸化インジウムにする。焼成温度は３００～１０００℃である。３００℃以上で完全な酸化物を得ることができ、１０００℃以下でＩＴＯ粒子間同士の激しい焼結を回避できる。好ましい焼成温度は３５０～８００℃以下である。焼成時間は０．１時間以上であればよいが、脱水反応が終了すれば、それ以上は不要である。雰囲気は大気とする。 In the firing step, firing is performed first, followed by reduction treatment. In firing, the tin-containing indium hydroxide is dehydrated to indium oxide. The firing temperature is 300 to 1000 ° C. A complete oxide can be obtained at 300 ° C. or higher, and intense sintering between ITO particles can be avoided at 1000 ° C. or lower. A preferable firing temperature is 350 to 800 ° C. or less. The firing time may be 0.1 hours or longer, but is not necessary once the dehydration reaction is completed. The atmosphere is air.
　焼成後の還元処理は、好ましくは２００～５００℃未満の温度で上述した弱還元雰囲気下で行われる。２００℃以上あれば酸素欠損を付与でき、５００℃未満であれば、適当な還元力が得られるので絶縁性のＩｎＯが生成されない。還元処理時間は０．５～５時間である。０．５時間未満では酸素欠損の形成が不十分であり、５時間を越えても優位な変化が見られない。以上の工程を経て、多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得ることができる。このように不活性ガスにアルコールを混合した混合ガスで焼成したＩＴＯ粉末では、粉末表面にＯＨ基が多いことから、後述する表面処理剤である珪酸エステル又はシランカップリング剤がこのＯＨ基と結合しやすいため、珪酸エステル又はシランカップリング剤による表面処理の効果がより高く、高温高湿下におけるＩＴＯ導電膜の電気抵抗値の上昇をより一層抑制することができる。 The reduction treatment after calcination is preferably performed at a temperature of 200 to 500 ° C. in the above-described weak reducing atmosphere. If it is 200 degreeC or more, an oxygen deficiency can be provided, and if it is less than 500 degreeC, since an appropriate reduction power is obtained, insulating InO is not produced | generated. The reduction treatment time is 0.5 to 5 hours. If it is less than 0.5 hours, oxygen deficiency is not sufficiently formed, and no significant change is observed even if it exceeds 5 hours. Through the above steps, an ITO powder composed of polycrystalline ITO particles can be obtained. Since ITO powder baked with a mixed gas in which alcohol is mixed with an inert gas in this manner has many OH groups on the powder surface, a silicate ester or silane coupling agent, which will be described later, binds to the OH group. Therefore, the effect of surface treatment with a silicate ester or a silane coupling agent is higher, and an increase in the electrical resistance value of the ITO conductive film under high temperature and high humidity can be further suppressed.
　＜ＩＴＯ導電膜形成用塗料の製造方法＞
　上記ＩＴＯ粉末を、分散媒のアルコール系溶液１００質量％に対して１～７０質量％の割合となるように混合し、ミキサーで攪拌することにより、ＩＴＯ導電膜形成用塗料を調製する。ＩＴＯ粉末の分散媒としては、エタノール、２－ブタノール、１－プロパノール等のアルコール系溶液が例示される。ＩＴＯ粉末はこのアルコール系溶液１００質量％に対して１～７０質量％の範囲で添加混合するとよい。１質量％未満では導電膜に十分な厚さの膜を形成するのが困難となり、７０質量％を越えると分散液の粘度が高く、塗布が困難となる。また必要に応じて上記ＩＴＯ導電膜形成用塗料をホモジェナイザーやビーズミル粉砕機等に入れて、この塗料中のＩＴＯ粉末を粉砕処理する。更に必要に応じて、抵抗を悪化させない範囲で、シリカゾルゲルやアクリル樹脂等のバインダを上記ＩＴＯ導電膜形成用塗料に添加することができる。 <Method for producing ITO conductive film forming paint>
The ITO powder is mixed so as to have a ratio of 1 to 70% by mass with respect to 100% by mass of the alcoholic solution of the dispersion medium, and stirred with a mixer to prepare an ITO conductive film forming coating material. Examples of the ITO powder dispersion medium include alcohol-based solutions such as ethanol, 2-butanol, and 1-propanol. The ITO powder may be added and mixed in the range of 1 to 70% by mass with respect to 100% by mass of the alcoholic solution. If the amount is less than 1% by mass, it is difficult to form a film having a sufficient thickness on the conductive film. If necessary, the ITO conductive film forming coating material is put in a homogenizer, a bead mill pulverizer or the like, and the ITO powder in the coating material is pulverized. Furthermore, if necessary, a binder such as silica sol gel or acrylic resin can be added to the ITO conductive film forming paint within a range not deteriorating the resistance.
　＜表面処理するまでのＩＴＯ導電膜の製造方法＞
　表面処理するまでのＩＴＯ導電膜は、例えば次のようにして製造される。予めＩＴＯ導電膜を形成するための基材を作製しておく。この基材は、片面にポリウレタンが塗布されたポリエチレンテレフタレート（ＰＥＴ）等の第１のフィルムであって、この第１のフィルムのうちポリウレタンが塗布されていない面をガラス基板上に両面粘着テープ等を用いて貼付けて作製される。先ず、ＩＴＯ導電膜形成用塗料を、ガラス基板上に固定された基材上にバーコート法、ダイコート法、ドクターブレード法等により塗布した後に、乾燥させる。次にＩＴＯ導電膜形成用塗料が塗布された基材をガラス基板から剥離し、基材のうちＩＴＯ導電膜形成用塗料の塗布面にＰＥＴ等の第２のフィルムを重ね合せ、この状態でロールプレス機にてロール圧力１００～２０００ｋｇ／ｃｍ、送り出し速度１０～５０ｃｍ／分の条件で圧力を加えた後に、第２のフィルムを剥離する。これによりフィルム上にＩＴＯ導電膜が形成される。 <Method for producing ITO conductive film until surface treatment>
The ITO conductive film until the surface treatment is produced, for example, as follows. A base material for forming the ITO conductive film is prepared in advance. This base material is a first film such as polyethylene terephthalate (PET) coated with polyurethane on one side, and the surface of the first film not coated with polyurethane is coated on a glass substrate with a double-sided adhesive tape or the like. Affixed using First, an ITO conductive film forming coating material is applied to a base material fixed on a glass substrate by a bar coating method, a die coating method, a doctor blade method, or the like, and then dried. Next, the base material coated with the ITO conductive film forming coating material is peeled off from the glass substrate, and a second film such as PET is superimposed on the surface of the base material on which the ITO conductive film forming coating material is applied. After applying pressure with a press machine under conditions of a roll pressure of 100 to 2000 kg / cm and a delivery speed of 10 to 50 cm / min, the second film is peeled off. Thereby, an ITO conductive film is formed on the film.
　＜ＩＴＯ導電膜の表面処理剤＞
　上記ＩＴＯ導電膜は表面処理剤により表面処理される。ここで、表面処理剤としては、炭素数が２以下であるアルコキシ基を４つ有する珪酸エステル又はこの珪酸エステルのオリゴマー体からなる表面処理剤、或いは炭素数が２以下であるアルコキシ基を２つ以上有し、かつアミノ基（-Ｒ-ＮＨ２、-Ｒ-ＮＨＲ、-Ｒ-ＮＲ１Ｒ２）若しくはメルカプト基（-Ｒ-ＳＨ）を末端基に有するアルキル基、炭素数が６以上である長鎖のアルキル基、又は一部がフッ素で置換されたアルキル基のいずれか１種のアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤が用いられる。ここでＲ、Ｒ１、Ｒ２はそれぞれアルキル基である。
　前記珪酸エステル又は珪酸エステルのオリゴマー体からなる表面処理剤によれば、多結晶ＩＴＯ導電膜表面に珪酸エステル又は珪酸エステルの加水分解体が結合した構成が得られる。また、前記シランカップリング剤からなる表面処理剤によれば、多結晶ＩＴＯ導電膜表面基にアミノ基又はメルカプト基が結合した構成、若しくは多結晶ＩＴＯ導電膜表面に（シランカップリング剤のアルコキシ基）又は（アルコキシ基の加水分解で生じたシラノール基）が結合した構成が得られる。多結晶ＩＴＯ導電膜表面の水酸基と表面処理剤との結合構成は、ＩＴＯ導電膜表面の－ＯＨを介するものである。 <Surface treatment agent for ITO conductive film>
The ITO conductive film is surface-treated with a surface treatment agent. Here, as the surface treatment agent, a surface treatment agent composed of a silicic acid ester having four alkoxy groups having 2 or less carbon atoms or an oligomer of this silicic acid ester, or two alkoxy groups having 2 or less carbon atoms. An alkyl group having an amino group (—R—NH 2, —R—NHR, —R—NR 1 R 2 ) or a mercapto group (—R—SH) as a terminal group, and having 6 or more carbon atoms A surface treatment agent comprising a silane coupling agent having one or more alkyl groups of any one of a long-chain alkyl group or an alkyl group partially substituted with fluorine is used. Here, R, R 1 and R 2 are each an alkyl group.
According to the surface treatment agent comprising the silicate ester or the silicate ester oligomer, a structure in which a silicate ester or a silicate hydrolyzate is bonded to the surface of the polycrystalline ITO conductive film is obtained. Further, according to the surface treatment agent comprising the silane coupling agent, a structure in which an amino group or a mercapto group is bonded to the surface of the polycrystalline ITO conductive film, or the surface of the polycrystalline ITO conductive film (an alkoxy group of the silane coupling agent). ) Or (silanol group generated by hydrolysis of alkoxy group) is bonded. The bonding configuration between the hydroxyl group on the surface of the polycrystalline ITO conductive film and the surface treatment agent is via —OH on the surface of the ITO conductive film.
　炭素数が２以下であるアルコキシ基を４つ有する珪酸エステルとしては、テトラメトキシシラン（炭素数１）、又はテトラエトキシシラン（炭素数２）が例示され、上記珪酸エステルのオリゴマーとしては、テトラメトキシシラン（炭素数１）の３～５量体、又はテトラエトキシシラン（炭素数２）の３～５量体が例示される。 Examples of the silicic acid ester having four alkoxy groups having 2 or less carbon atoms include tetramethoxysilane (carbon number 1) or tetraethoxysilane (carbon number 2). Examples are silane (carbon number 1) trimer to pentamer or tetraethoxysilane (carbon number 2) trimer to pentamer.
　また炭素数が２以下であるアルコキシ基を２つ以上有し、かつアミノ基若しくはメルカプト基を末端基に有するアルキル基を１つ以上有するシランカップリング剤としては、Ｎ－２－(アミノエチル)－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、又は３－メルカプトプロピルトリメトキシシランが例示される。 A silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups having an amino group or a mercapto group as a terminal group includes N-2- (aminoethyl) Examples are -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, or 3-mercaptopropyltrimethoxysilane.
　また炭素数が２以下であるアルコキシ基を２つ以上有し、かつ炭素数が６以上の長鎖のアルキル基を１つ以上有するシランカップリング剤としては、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン又はデシルトリメトキシシランが例示される。 Examples of the silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more long-chain alkyl groups having 6 or more carbon atoms include hexyltrimethoxysilane and hexyltriethoxysilane. Or decyltrimethoxysilane is illustrated.
　更に炭素数が２以下であるアルコキシ基を２つ以上有し、かつ一部にフッ素で置換されたアルキル基を１つ以上有するシランカップリング剤としては、トリフルオロプロピルトリメトキシシランが例示される。なお、本発明の珪酸エステルは、ＩＴＯ粒子表面に結合した後、ＳｉＯ２としてネットワークを組みやすい、複数のエステル結合を持つものが好ましい。 Further, trifluoropropyltrimethoxysilane is exemplified as the silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups partially substituted with fluorine. . The silicate ester of the present invention preferably has a plurality of ester bonds that can easily form a network as SiO 2 after being bonded to the surface of the ITO particles.
　＜ＩＴＯ導電膜の表面処理方法（表面処理を含むＩＴＯ導電膜の製造方法）＞
（１）表面処理剤の気相暴露法
　先ず、表面処理剤の濃度が１０～１００質量％となるようにこの表面処理剤を溶剤に溶解して表面処理液を作製する。この溶剤には、アルコール、ケトン、水又はこれらを含む混合溶媒を用いることができる。次いで、この表面処理液中で２０～１５０℃に予熱した窒素ガスをバブリングすることにより、窒素ガスに表面処理剤を含ませる。内容積５Ｌのガラス製の容器に、上記の方法で作製したＩＴＯフィルムを入れ、表面処理剤の蒸気を含ませたガスを、０．１～５Ｌ／分で１～１８０分間流通させることにより、ＩＴＯフィルムの表面処理を行う。表面処理剤の濃度、ガス流量、流通時間、ガス温度がそれぞれ上記下限値未満では十分な表面処理効果が得られず、上記上限値を超えると、表面処理効果が得られないと同時に、表面処理液がＩＴＯ膜表面に結露し易く、好ましくない。 <Surface Treatment Method for ITO Conductive Film (Method for Producing ITO Conductive Film Including Surface Treatment)>
(1) Gas Phase Exposure Method for Surface Treatment Agent First, a surface treatment solution is prepared by dissolving the surface treatment agent in a solvent so that the concentration of the surface treatment agent is 10 to 100% by mass. As this solvent, alcohol, ketone, water, or a mixed solvent containing these can be used. Next, a surface treatment agent is included in the nitrogen gas by bubbling nitrogen gas preheated to 20 to 150 ° C. in the surface treatment liquid. By placing the ITO film produced by the above method in a glass container having an internal volume of 5 L and circulating a gas containing the surface treatment agent vapor at 0.1 to 5 L / min for 1 to 180 minutes, Surface treatment of ITO film is performed. If the concentration of the surface treatment agent, the gas flow rate, the circulation time, and the gas temperature are less than the above lower limit values, sufficient surface treatment effect cannot be obtained. The liquid tends to condense on the ITO film surface, which is not preferable.
（２）表面処理剤の塗布法
　塗布法の代表例として、スピンコート法及びディップコート法を説明する。スピンコート法では、先ず、表面処理剤の濃度が０．１～１０質量％となるようにこの表面処理剤を溶剤に溶解して表面処理液を作製する。この溶剤には、アルコール、ケトン、水又はこれらを含む混合溶媒を用いることができる。次いで、上記の方法で作製したＩＴＯフィルムを水平に配置して回転させ、その表面に上記表面処理液を滴下することにより、ＩＴＯフィルムの表面処理を行う。表面処理剤の濃度が上記下限値未満では表面処理効果が十分に得られず、上記上限値を超えると過剰な表面処理液がフィルム上に残留することで、ＩＴＯ膜にムラが生じてしまうため、好ましくない。スピコートの回転速度は好ましくは１００～５０００ｒｐｍであるが、膜にムラが生じない範囲であれば、この範囲に限定されない。 (2) Coating method of surface treatment agent A spin coating method and a dip coating method will be described as representative examples of the coating method. In the spin coating method, first, a surface treatment solution is prepared by dissolving the surface treatment agent in a solvent so that the concentration of the surface treatment agent is 0.1 to 10% by mass. As this solvent, alcohol, ketone, water, or a mixed solvent containing these can be used. Next, the ITO film produced by the above method is horizontally disposed and rotated, and the surface treatment liquid is dropped onto the surface of the ITO film to perform surface treatment of the ITO film. If the concentration of the surface treatment agent is less than the lower limit value, the surface treatment effect cannot be sufficiently obtained, and if the concentration exceeds the upper limit value, an excessive surface treatment liquid remains on the film, resulting in unevenness in the ITO film. It is not preferable. The rotation speed of the spout is preferably 100 to 5000 rpm, but is not limited to this range as long as the film does not cause unevenness.
　次にディップコート法を説明する。先ず、表面処理剤の濃度が０．０１～１０質量％となるようにこの表面処理剤を溶剤に溶解して表面処理液を作製する。この溶剤には、アルコール、ケトン、水又はこれらを含む混合溶媒を用いることができる。次いで、この表面処理液中に、上記の方法で作製したＩＴＯフィルムを０．１～６０分間浸漬（ディッピング）した後、乾燥させることにより、ＩＴＯフィルムの表面処理を行う。表面処理剤の濃度が上記下限値未満では表面処理効果が十分に得られず、上記上限値を超えると過剰な表面処理液がフィルム上に残留し、これによりＩＴＯ膜に処理ムラが生じてしまうため、好ましくない。乾燥には特に制限はないが、残液によりムラが生じやすいことから、エアガン等で残液を吹き飛ばすことが好ましい。なお、塗布法は、スピンコート法、ディップコート法に限らず、他のコーティング法も本発明に用いることができる。 Next, the dip coating method will be explained. First, a surface treatment solution is prepared by dissolving the surface treatment agent in a solvent so that the concentration of the surface treatment agent is 0.01 to 10% by mass. As this solvent, alcohol, ketone, water, or a mixed solvent containing these can be used. Next, the ITO film produced by the above method is immersed (dipped) in this surface treatment solution for 0.1 to 60 minutes, and then dried to perform surface treatment of the ITO film. When the concentration of the surface treatment agent is less than the above lower limit value, the surface treatment effect cannot be sufficiently obtained, and when the concentration exceeds the above upper limit value, an excessive surface treatment liquid remains on the film, thereby causing uneven treatment on the ITO film. Therefore, it is not preferable. Although there is no restriction | limiting in particular in drying, Since nonuniformity arises easily with a residual liquid, it is preferable to blow off a residual liquid with an air gun etc. The coating method is not limited to the spin coating method and the dip coating method, and other coating methods can be used in the present invention.
　＜ＩＴＯ導電膜の評価方法＞
　上記のように表面処理された透明導電膜について、以下のようにして表面抵抗の評価を行った。即ち、上記のように表面処理された透明導電膜の予め定められた測定点につき、三菱油化製ＬｏｒｅｓｔａＡＰ ＭＣＰ－Ｔ４００を用いて表面の電気抵抗を測定し、その測定値を初期電気抵抗値とした。その後、８５℃、相対湿度８５％ＲＨに制御された恒温恒湿槽内に、２０００時間透明導電膜を保管した後に、初期抵抗測定時に定めた測定点において再度表面の電気抵抗の値を測定し、これを加湿後電気抵抗値とした。そして、下記式に基づいて変化率を算出した。なお、ここで相対湿度は大気圧下、温度８５℃／湿度８５％における相対湿度である。
　　　　　　変化率 ＝ [加湿後電気抵抗値／ 初期電気抵抗値] <Evaluation method of ITO conductive film>
About the transparent conductive film surface-treated as mentioned above, surface resistance was evaluated as follows. That is, for the predetermined measurement points of the transparent conductive film surface-treated as described above, the electrical resistance of the surface was measured using LorestaAP MCP-T400 manufactured by Mitsubishi Yuka Co., Ltd., and the measured value was regarded as the initial electrical resistance value. did. Then, after storing the transparent conductive film for 2000 hours in a constant temperature and humidity chamber controlled to 85 ° C. and relative humidity 85% RH, the value of the electrical resistance of the surface is measured again at the measurement point determined at the time of initial resistance measurement. This was used as the electric resistance value after humidification. And the rate of change was computed based on the following formula. Here, the relative humidity is relative humidity at a temperature of 85 ° C./humidity of 85% under atmospheric pressure.
Rate of change = [electric resistance value after humidification / initial electric resistance value]
　次に本発明の実施例を比較例とともに詳しく説明する。 Next, examples of the present invention will be described in detail together with comparative examples.
　＜実施例１～１２、比較例１～６＞
　前述した方法で、多結晶ＩＴＯ粒子の平均長さＬが１μｍ、平均直径Ｄが０．２μｍであるスズ含有水酸化インジウムの針状粒子を作製した。この針状粒子の作製に際し、前述した超音波の周波数は３４ｋＨｚであり、その付与時間は６０分であり、スズ及びインジウムの塩は塩酸塩であり、アルカリはアンモニアである。得られたケーキを１１０℃で乾燥した。焼成は窒素の不活性ガス雰囲気で、６００℃、３時間行った。焼成後の還元処理は、水素を３％添加した窒素ガス雰囲気で、３００℃、２時間行った。 <Examples 1 to 12, Comparative Examples 1 to 6>
By the method described above, needle-like particles of tin-containing indium hydroxide having an average length L of polycrystalline ITO particles of 1 μm and an average diameter D of 0.2 μm were prepared. In producing the acicular particles, the frequency of the ultrasonic wave described above is 34 kHz, the application time is 60 minutes, the salt of tin and indium is hydrochloride, and the alkali is ammonia. The resulting cake was dried at 110 ° C. Firing was performed at 600 ° C. for 3 hours in an inert gas atmosphere of nitrogen. The reduction treatment after firing was performed at 300 ° C. for 2 hours in a nitrogen gas atmosphere to which 3% of hydrogen was added.
　こうして得られたＩＴＯ粉末を、分散媒に対して２５質量％の割合となるように添加混合し、超音波ホモジェナイザーで３０分間攪拌して分散させることにより、ＩＴＯ導電膜形成用塗料を調製した。このＩＴＯ導電膜形成用塗料を、前述した透明導電膜の製造方法に従って、ＰＥＴフィルム上に、バーコート法で成膜し、この膜にロール圧力７００ｋｇ／ｃｍ、送り出し速度３０ｃｍ／分で圧力を加えることで、ＰＥＴフィルム上に形成されたＩＴＯ導電膜を得た。 The ITO powder thus obtained is added and mixed so that the ratio is 25% by mass with respect to the dispersion medium, and is stirred and dispersed with an ultrasonic homogenizer for 30 minutes to prepare a coating for forming an ITO conductive film. did. This ITO conductive film forming coating is formed on a PET film by a bar coating method in accordance with the method for producing a transparent conductive film described above, and pressure is applied to this film at a roll pressure of 700 kg / cm and a delivery speed of 30 cm / min. Thus, an ITO conductive film formed on the PET film was obtained.
　このようにして得られたＩＴＯ導電膜を５ｃｍ×５ｃｍの大きさに切り出して、表１に示す表面処理剤を用いて、前述した処理法で表面処理した。このとき、気相暴露法による表面処理は、ガラス製の容器に上記の方法で作製したＩＴＯフィルムを入れ、表面処理剤の蒸気を含ませたガスを、０．５Ｌ／分で６０分間流通させることにより行った。このガスは、８０℃の予熱した窒素ガスを、表面処理液中でバブリングすることにより、窒素ガスに表面処理剤を含ませて得たものである。スピンコート法による表面処理は、表面処理剤の濃度が1質量％となるようにエタノールで希釈した表面処理液を、上記の方法で作製した５ｃｍ角のＩＴＯフィルムに５００μｌ滴下し、５００ｒｐｍで６０秒間回転させることにより行った。ディップコート法（浸漬法）による表面処理は、表面処理剤の濃度が1質量％となるようにエタノールで希釈した表面処理液に、上記の方法で作製した５ｃｍ角のＩＴＯフィルムを１分間浸漬した後に、エアガンで残液を吹き飛ばし、室温で乾燥させた。 The ITO conductive film thus obtained was cut into a size of 5 cm × 5 cm and surface-treated with the above-described treatment method using the surface treatment agent shown in Table 1. At this time, in the surface treatment by the vapor phase exposure method, the ITO film produced by the above method is put in a glass container, and the gas containing the vapor of the surface treatment agent is circulated at 0.5 L / min for 60 minutes. Was done. This gas is obtained by bubbling a preheated nitrogen gas at 80 ° C. in a surface treatment liquid so that the surface treatment agent is included in the nitrogen gas. In the surface treatment by the spin coating method, 500 μl of a surface treatment solution diluted with ethanol so that the concentration of the surface treatment agent is 1% by mass is dropped on the 5 cm square ITO film prepared by the above method, and then at 500 rpm for 60 seconds. This was done by rotating. In the surface treatment by the dip coating method (immersion method), the 5 cm square ITO film prepared by the above method was immersed for 1 minute in a surface treatment solution diluted with ethanol so that the concentration of the surface treatment agent was 1% by mass. Later, the remaining liquid was blown off with an air gun and dried at room temperature.
　＜比較試験１及び評価＞
　実施例１～１２及び比較例１～６の表面処理されたＩＴＯ導電膜を前述した評価方法に基づいて、各膜毎に初期電気抵抗値と加湿後電気抵抗値を測定した。そのうえで、加湿後電気抵抗値を初期電気抵抗値で除して変化率を求めた。その結果を表１に示す。 <Comparative test 1 and evaluation>
The surface-treated ITO conductive films of Examples 1 to 12 and Comparative Examples 1 to 6 were measured for the initial electric resistance value and the electric resistance value after humidification for each film based on the evaluation method described above. Then, the rate of change was determined by dividing the electrical resistance value after humidification by the initial electrical resistance value. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から明らかなように、表面処理なしのＩＴＯ導電膜の比較例１では、加湿後電気抵抗値が１４９５７Ω／sq (ohms per square)と大きくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が５０．６倍と大きくなった。これに対し、テトラメトキシシラン、テトラメトキシシランの３～５量体、テトラエトキシシラン及びテトラエトキシシランの３～５量体で表面処理したＩＴＯ導電膜の実施例１～４では、加湿後電気抵抗値が１９１０～３１６３Ω／sqと小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が６．１～９．７倍と小さくなった。これにより炭素数が２以下であるアルコキシ基を４つ有する珪酸エステルからなる表面処理剤により、又はこれらの珪酸エステルのオリゴマー体からなる表面処理剤により、表面処理されたＩＴＯ導電膜は、加湿後電気抵抗値が比較的低く、かつ高温高湿下であっても、電気抵抗値の上昇を十分に抑制できることが判った。 As is clear from Table 1, in Comparative Example 1 of the ITO conductive film without surface treatment, the electric resistance value after humidification becomes large as 14957 Ω / sq (ohms per square), and from the initial electric resistance value to the electric resistance value after humidification. The rate of change of was increased to 50.6 times. In contrast, in Examples 1 to 4 of the ITO conductive film surface-treated with tetramethoxysilane, tetramethoxysilane trimer to pentamer, tetraethoxysilane and tetraethoxysilane trimer to pentamer, electric resistance after humidification was obtained. The value decreased from 1910 to 3163 Ω / sq, and the rate of change from the initial electrical resistance value to the electrical resistance value after humidification decreased from 6.1 to 9.7 times. As a result, the ITO conductive film surface-treated with a surface treatment agent comprising a silicate ester having four alkoxy groups having 2 or less carbon atoms or a surface treatment agent comprising an oligomer of these silicate esters is obtained after humidification. It has been found that the increase in the electric resistance value can be sufficiently suppressed even when the electric resistance value is relatively low and the temperature and humidity are high.
　また、表１から明らかなように、アミノ基を末端基ではなく中央に有するヘキサメチルジシラザンで表面処理したＩＴＯ導電膜の比較例４では、加湿後電気抵抗値が２１３１３Ω／sqと大きくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が４９．２倍と大きくなった。これに対し、アミノ基を末端基に有するＮ－２－(アミノエチル)－３－アミノプロピルトリメトキシシラン、及び３－アミノプロピルトリメトキシシランで表面処理したＩＴＯ導電膜の実施例５及び６では、加湿後電気抵抗値が８２３Ω／sq及び６０２Ω／sqと小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が２．６倍及び２．１倍と小さくなった。またメルカプト基を末端基に有する３－メルカプトプロピルメチルジメトキシシラン、及び３－メルカプトプロピルトリメトキシシランで表面処理したＩＴＯ導電膜の実施例７及び８では、加湿後電気抵抗値が７３９Ω／sq及び６２４Ω／sqと小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が２．３倍及び１．８倍と小さくなった。これにより炭素数が２以下であるアルコキシ基を２つ以上有し、かつアミノ基若しくはメルカプト基を末端基に有するアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤により、表面処理されたＩＴＯ導電膜は、加湿後電気抵抗値が比較的低く、かつ高温高湿下であっても、電気抵抗値の上昇を十分に抑制できることが判った。 Further, as is apparent from Table 1, in Comparative Example 4 of the ITO conductive film surface-treated with hexamethyldisilazane having an amino group at the center instead of a terminal group, the electric resistance value after humidification was increased to 21313 Ω / sq, The rate of change from the initial electrical resistance value to the electrical resistance value after humidification was as large as 49.2 times. In contrast, in Examples 5 and 6 of the ITO conductive film surface-treated with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane having an amino group as a terminal group and 3-aminopropyltrimethoxysilane, The electric resistance values after humidification were reduced to 823 Ω / sq and 602 Ω / sq, and the rate of change from the initial electric resistance value to the electric resistance value after humidification was reduced to 2.6 times and 2.1 times. In Examples 7 and 8 of the ITO conductive film surface-treated with 3-mercaptopropylmethyldimethoxysilane having a mercapto group as a terminal group and 3-mercaptopropyltrimethoxysilane, the electric resistance values after humidification were 739Ω / sq and 624Ω. / Sq, and the rate of change from the initial electrical resistance value to the electrical resistance value after humidification was reduced to 2.3 times and 1.8 times. Thus, the surface treatment is performed by the surface treatment agent comprising a silane coupling agent having at least two alkoxy groups having 2 or less carbon atoms and at least one alkyl group having an amino group or a mercapto group as a terminal group. It has been found that the ITO conductive film has a relatively low electrical resistance value after humidification and can sufficiently suppress an increase in the electrical resistance value even under high temperature and high humidity.
　また、表１から明らかなように、炭素数が６以上である長鎖のアルキル基を有しないビニルトリメトキシシラン、ｐ－スチリルメトキシシラン、フェニルトリメトキシシラン、及びジメチルジメトキシシランで表面処理したＩＴＯ導電膜の比較例２、３、５及び６では、加湿後電気抵抗値が１１０１４～１４２０４Ω／sqと大きくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が２９．８～４２．０倍と大きくなった。これに対し、炭素数が６以上である長鎖のアルキル基を有するヘキシルトリメトキシシラン、デシルトリメトキシシラン及びヘキシルトリエトキシシランで表面処理したＩＴＯ導電膜の実施例１０、１１及び１２では、加湿後電気抵抗値が１０２５～１４７３Ω／sqと小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が３．１～４．５倍と小さくなった。これにより炭素数が２以下であるアルコキシ基を２つ以上有し、かつ炭素数が６以上である長鎖のアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤により、表面処理されたＩＴＯ導電膜は、加湿後電気抵抗値が比較的低く、かつ高温高湿下であっても、電気抵抗値の上昇を十分に抑制できることが判った。 Further, as apparent from Table 1, ITO surface-treated with vinyltrimethoxysilane, p-styrylmethoxysilane, phenyltrimethoxysilane, and dimethyldimethoxysilane having no long-chain alkyl group having 6 or more carbon atoms. In Comparative Examples 2, 3, 5 and 6 of the conductive film, the electric resistance value after humidification was increased to 11014 to 14204 Ω / sq, and the rate of change from the initial electric resistance value to the electric resistance value after humidification was 29.8 to 42.42. Increased to 0 times. On the other hand, in Examples 10, 11 and 12 of the ITO conductive film surface-treated with hexyltrimethoxysilane, decyltrimethoxysilane and hexyltriethoxysilane having a long-chain alkyl group having 6 or more carbon atoms, humidification was performed. The post-electric resistance value decreased to 1025 to 1473 Ω / sq, and the rate of change from the initial electric resistance value to the post-humidified electric resistance value decreased to 3.1 to 4.5 times. Thus, the surface treatment is performed by the surface treatment agent comprising a silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more long-chain alkyl groups having 6 or more carbon atoms. It has been found that the ITO conductive film has a relatively low electrical resistance value after humidification and can sufficiently suppress an increase in the electrical resistance value even under high temperature and high humidity.
　更に、表１から明らかなように、一部がフッ素で置換されたアルキル基を有するトリフルオロプロピルトリメトキシシランで表面処理したＩＴＯ粉末を用いてＩＴＯ導電膜を形成した実施例９では、加湿後電気抵抗値が９６４Ω／sqと小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が３．５倍と小さくなった。これにより炭素数が２以下であるアルコキシ基を２つ以上有し、かつ一部がフッ素で置換されたアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤により、表面処理されたＩＴＯ導電膜は、加湿後電気抵抗値が比較的低く、かつ高温高湿下であっても、電気抵抗値の上昇を十分に抑制できることが判った。 Furthermore, as apparent from Table 1, in Example 9 in which the ITO conductive film was formed using ITO powder surface-treated with trifluoropropyltrimethoxysilane having an alkyl group partially substituted with fluorine, The electrical resistance value was reduced to 964Ω / sq, and the rate of change from the initial electrical resistance value to the electrical resistance value after humidification was reduced to 3.5 times. As a result, ITO surface-treated with a surface treatment agent comprising a silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups partially substituted with fluorine. It has been found that the conductive film has a relatively low electrical resistance value after humidification and can sufficiently suppress an increase in the electrical resistance value even under high temperature and high humidity.
　１０　　多結晶ＩＴＯ粒子
　１１　　棒状中心核
　１２　　棒状体 10 Polycrystalline ITO particles 11 Rod-shaped central core 12 Rod-shaped body

Claims (6)

  1. 　炭素数が２以下であるアルコキシ基を４つ有する珪酸エステル又はこの珪酸エステルのオリゴマー体からなる表面処理剤により、或いは炭素数が２以下であるアルコキシ基を２つ以上有し、かつアミノ基若しくはメルカプト基を末端基に有するアルキル基、炭素数が６以上である長鎖のアルキル基、又は一部がフッ素で置換されたアルキル基のいずれか１種のアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤により、表面処理されたＩＴＯ導電膜。 By a surface treatment agent comprising a silicic acid ester having 4 or less alkoxy groups having 2 or less carbon atoms or an oligomer of this silicic acid ester, or having 2 or more alkoxy groups having 2 or less carbon atoms, and an amino group or Silane coupling having one or more alkyl groups of any one of an alkyl group having a mercapto group as a terminal group, a long-chain alkyl group having 6 or more carbon atoms, or an alkyl group partially substituted with fluorine ITO conductive film surface-treated with a surface treatment agent comprising an agent.
  2. 　前記珪酸エステルが、炭素数が１のアルキル基を有するテトラメトキシシラン、又は炭素数が２のアルキル基を有するテトラエトキシシランである請求項１に記載のＩＴＯ導電膜。 The ITO conductive film according to claim 1, wherein the silicate ester is tetramethoxysilane having an alkyl group having 1 carbon atom or tetraethoxysilane having an alkyl group having 2 carbon atoms.
  3. 　前記シランカップリング剤が、Ｎ－２－(アミノエチル)－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、及びデシルトリメトキシシランからなる群より選択される何れか一つである請求項１に記載のＩＴＯ導電膜。 The silane coupling agent is N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, trifluoro 2. The ITO conductive film according to claim 1, which is any one selected from the group consisting of propyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and decyltrimethoxysilane.
  4. 　請求項１ないし３のいずれか１項に記載の表面処理剤を溶剤に溶解した表面処理液の蒸気を容器に入れたＩＴＯ導電膜に気相暴露することによりＩＴＯ導電膜の表面を処理するＩＴＯ導電膜の製造方法。 The ITO which processes the surface of an ITO electrically conductive film by carrying out vapor phase exposure to the ITO electrically conductive film which put the vapor | steam of the surface treating liquid which melt | dissolved the surface treating agent of any one of Claim 1 thru | or 3 in the solvent in the container Manufacturing method of electrically conductive film.
  5. 　請求項１ないし３のいずれか１項に記載の表面処理剤を溶剤に溶解した表面処理液をＩＴＯ導電膜の表面に塗布することによりＩＴＯ導電膜の表面を処理するＩＴＯ導電膜の製造方法。 A method for producing an ITO conductive film, wherein the surface of an ITO conductive film is treated by applying a surface treatment solution obtained by dissolving the surface treatment agent according to any one of claims 1 to 3 in a solvent to the surface of the ITO conductive film.
  6. 　前記表面処理液のＩＴＯ導電膜の表面への塗布がスピンコート法又はディップコート法により行われる請求項５に記載のＩＴＯ導電膜の製造方法。 The method for producing an ITO conductive film according to claim 5, wherein the surface treatment liquid is applied to the surface of the ITO conductive film by a spin coating method or a dip coating method.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08165147A (en) * 1994-12-13 1996-06-25 Mitsubishi Materials Corp Low reflecting/electromagnetic shielding transparent electroconductive film and coating compound for forming the same film
JPH09263716A (en) * 1996-03-29 1997-10-07 Mitsubishi Materials Corp Overcoat composition for transparent electrically conductive film excellent in electical conductivity
JP2005166350A (en) * 2003-12-01 2005-06-23 Ulvac Japan Ltd Transparent electrode for flat panel display, coating liquid for forming transparent conductive film and forming method of transparent electrode
JP2010020951A (en) * 2008-07-09 2010-01-28 Kaneka Corp Method for manufacturing transparent conductive film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08165147A (en) * 1994-12-13 1996-06-25 Mitsubishi Materials Corp Low reflecting/electromagnetic shielding transparent electroconductive film and coating compound for forming the same film
JPH09263716A (en) * 1996-03-29 1997-10-07 Mitsubishi Materials Corp Overcoat composition for transparent electrically conductive film excellent in electical conductivity
JP2005166350A (en) * 2003-12-01 2005-06-23 Ulvac Japan Ltd Transparent electrode for flat panel display, coating liquid for forming transparent conductive film and forming method of transparent electrode
JP2010020951A (en) * 2008-07-09 2010-01-28 Kaneka Corp Method for manufacturing transparent conductive film

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